part i chemical basics

Part IChemical Basics

Applied Homogeneous Catalysis, First Edition. Arno Behr and Peter Neubert.� 2012 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2012 by Wiley-VCH Verlag GmbH & Co. KGaA.

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1

Definition, Options, and Examples

What Actually Is Catalysis?

1.1Definition of Catalysis

Let us consider a reversible chemical reac-tion between the eductsA andBwhich leadsto the products C and D:

AþBKCþD ð1:1Þ

A typical example is the formation of anester from a carboxylic acid and an alcohol,which involves the elimination of water,while the reverse reaction involves thehydrolysis of an ester to a carboxylic acidand an alcohol:

R�COOHþR0 �OHKR�COOR0þH2O

ð1:2Þ

The steady state of this reaction –

depending on pressure and temperature –is controlled by Nature and determinedby the thermodynamics (cf. Chapter 10).The rate at which equilibrium is achievedis described by kinetics (cf. Chapter 11).As is well known from organic chemistry,the reaction requires a small amount ofsulfuric acid to get it started. Then, if thewater produced is removed constantlyfrom the reaction vessel, the ester can

be obtained in quantitative amounts. Inthis case, the sulfuric acid serves as a�catalyst.�Another example is the highly exother-

mic reaction of the two gases hydrogen andoxygen. In a sealed vessel, they can bemixedto any ratio without reaction, but if a smallamount of a platinumsponge is added to themixture it reacts spontaneously. The cata-lyst, with its large surface area, initiates theso-called �hydrogen–oxygen reaction�:

H2 þ 0:5 O2 KH2O ð1:3Þ

The reaction heat indicates a thermody-namically permitted reaction that will pro-ceed even at room temperature and at lowpressure. This reaction also requires a cat-alyst – the transitionmetal, platinum– to getit started: only the catalyst is able to run thereaction.The adjuvant effect of the platinum

sponge was first discovered by JohannWolfgang D€obereiner (Figure 1.1) who, onthe 27th of July 1823, used a platinumsponge to construct a gas lighter (Fig-ure 1.2). In the lighter, the crank, e, is usedto dip a piece of zinc into a tank, c, whichcontains sulfuric acid; this leads to theformation of hydrogen (Eq. (1.4)):

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Applied Homogeneous Catalysis, First Edition. Arno Behr and Peter Neubert.� 2012 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2012 by Wiley-VCH Verlag GmbH & Co. KGaA.

Znþ 2Hþ !Zn2þ þH2 ð1:4Þ

The hydrogen is first collected in anupright pipe and then released from thepipe�s upper end through a simultaneouslyopened valve. The hydrogen is mixed withoxygen from the ambient air and ignited bya piece of platinum sponge, f, attachedimmediately above the valve. The first auto-matic gas lighter had been invented!D€obereiner gave one of these lighters to his

namesake, Goethe, who initially had pro-blems using it. In 1828, Goethe wrote toD€obereiner:

�Ew. Hochwohlgeboren haben dieGef€alligkeit gehabt, einen dem Anblick undZweck nach sehr anmutigen Apparatzuzusenden, aber ich will nur gestehen, daßohngeachtet der genauen beigef€ugtenBeschreibung ich doch das Experiment nichtzu unternehmen getraue.�

(Approximate English translation: Yourhonor has been so kind to send me the verycharming apparatus; however, I have toadmit that I don�t feel able to carry out theexperiment.)However, some time later Goethe is said

to have used the lighter on a regular basis.The first definition of a catalyst was pro-

vided in 1836 by the Swedish chemist J€onsJakob Berzelius (Figure 1.3) of the Univer-sity of Stockholm, who noted that:

�The substances that cause thedecomposition of H2O2 do not achieve thisgoal by being incorporated into the newcompounds (H2OandO2); in each case theyremain unchanged and hence act by meansof an inherent force whose nature is stillunknown. . .

(Berzelius meant that, in the case of thehydrogen–oxygen reaction, the �substance�– the platinum sponge – would wakenthe �dozing� gases hydrogen and oxygen.

Figure 1.1 JohannWolfgang D€obereiner.

Figure 1.2 D€obereiner�s gas lighter.Figure 1.3 J€ons JakobBerzelius.

4j 1 Definition, Options, and Examples

However, hewas unclear about the details ofthe processes driven by the catalyst.)Berzelius used the term �katalysis�, which

is derived from the Greek, meaning �tountie,� and on that basis he considered thebond-breaking stage to be the crucial step. Incontrast, the Chinese took a somewhat dif-ferentapproachtocatalysis; theChinesechar-acter �tschu mei� (Figure 1.4) means bothcatalysis and �marriage broker,� with theemphasis being placed much more on thelinking properties.When considering today�s definition of a

catalyst:

. A catalyst is a substance that increasesthe rate at which a chemical systemreaches its equilibrium.

. A catalyst participates in a chemicalreaction, but is not itself consumed.

Although, in theory, a catalyst should beactive �for ever,� there is of course no ideal�philosopher�s stone.� Whilst each catalysthas a certain lifetime, during which it willcatalyze a reaction in aneconomical fashion,its efficiency will decrease steadily until,ultimately, it is �dead.� The lifetime of acatalystmaybeveryshort,or itmaybeseveralyears (this point is described in detail inChapter 4).One factor that all catalysts have in com-

mon is that, immediately after they havesuccessfully catalyzed a first reaction, theyare available to catalyze another reaction.

Moreover, this action can be repeatedmanythousands or even millions of times. Themost commonly used method used to rep-resent this behavior graphically is a circle;this is often referred to as �catalytic cycle.�A generalized type of cycle incorporatingthe addition reaction A þ B ! A�B, cat-alyzed by C, is shown in Figure 1.5.Here, the catalyst C first adds reactant

A and, subsequently, also reactant B. The tworeactantsareunited in the immediate vicinityof the catalyst (the �marriage broker�), suchthat a new product, A–B, is formed. Thecatalyst remains in the condition it was inat the start of the cycle and, therefore, isavailable for another cycle.

1.2The Different Varieties of Catalysis

The reaction in Eq. (1.2) contains liquidreactants – carboxylic acid and alcohol –which are reacted to produce a liquid esterin the presence of liquid sulfuric acid. All ofthe components are completely soluble and,as there is only one homogeneous liquidphase in the vessel, this is referred to ashomogeneous catalysis.In contrast, in Eq. (1.3) two gases react

in the presence of a solid catalyst, theplatinum sponge. In this type of catalysisthere are at least two phases, and some-times even three (gaseous, liquid, andsolid). Based on such heterogeneity, thisvariant is referred to as heterogeneouscatalysis.

Figure 1.4 The Chinese character forcatalysis and matchmaker (�tschu mei�). Figure 1.5 A general catalysis cycle.

1.2 The Different Varieties of Catalysis j5

There are, however, different subtypes ofthe two variants, depending on the type ofcatalyst being used.

Homogeneous catalysts These can be:. soluble acids or bases) homogeneousacid/base catalysis

. organic compounds ) homogeneousorganocatalysis

. soluble enzymes ) homogeneousenzyme or biocatalysis

. soluble transition metal salts or solubletransition metal complexes )homogeneous transition metal catalysis.

Heterogeneous catalysts These can be:. insoluble acids or bases )heterogeneous acid/base catalysis

. solid immobilized enzymes )heterogeneous enzyme catalysis

. solid metals or metal oxides )heterogeneous metal catalysis.

The main subject of this book is homoge-neous transition metal catalysis, which pro-vides excellent opportunities for both gentleandselective reactions. In fact, suchcatalysisoffers a range of benefits compared to

heterogeneous catalysis (see Table 1.1).Unfortunately, however, homogeneoustransition metal catalysis has one inherentdisadvantage thatderivesfromitsdefinition;that is, as all of the reactants, catalysts andproducts are in the same homogeneousphase during reaction, any subsequent sep-arationof the catalyst for its reusecanbeverydifficult. Catalyst separation is, nonetheless,essential as the typically very expensive tran-sition metal catalyst must be recycleduncompromisingly for economic reasons,and not discharged with the product.Likewise, for ecological reasons, neither

the transition metal compounds nor anyassociated organic compounds must bereleased into the environment. For exam-ple, although nickel is an important catalystmetal, many people will suffer an allergicresponse if they come into contact with it.Because of these problems, several chaptersof this book relate to separation conceptsassociated with homogeneous catalysis (seeChapters 14 to 18).Homogeneous transition metal catalysts are

usually well-defined compounds; typically,their chemical composition is well knownand their structure can be determined easily

Table 1.1 Comparison of homogeneous and heterogeneous catalysis.

Criterion Heterogeneous catalysis Homogeneous catalysis

Catalyst stoichiometry Often undefined CommonCatalyst structure Often undefined CommonCatalyst variability Little Very variableCatalyst reproducibility Often difficult Very highMechanism knowledge Often very little AvailableNumber of active centers Only surface atoms All metal atomsCatalyst activity Different HighCatalyst selectivity Usually poor Usually highDiffusion problems Present Barely presentConditions Often harsh Usually mildCatalyst lifetime Different DifferentDeactivation through poisoning Common RarelySeparation and recycling Usually easy Difficult


by using various spectroscopic methods.Such catalysts can be synthesized accordingto definite, reproducible synthetic protocols.A typical example of a homogeneous tran-sition metal catalyst is Wilkinson�s catalyst[Rh(PPh3)3Cl], named after the Nobel prizelaureate Sir Geoffrey Wilkinson (Figure 1.6),fromImperialCollege, London.This catalystcan be easily and reproducibly prepared inhigh yields from rhodium trichloridehydrate and triphenylphosphine PPh3 inethanol. Furthermore, variations can easilybe achieved in its electronic and steric prop-erties, by using different phosphine ligands.Moreover, its functionality – for example, inthehydrogenationof olefinic double bonds–has been investigated thoroughly, duemainly to the good analytical options avail-able during homogeneous catalysis (seeChapter 12).A typicalexampleof aheterogeneous catalyst

is the�ammonia catalyst,�whichcatalyzes theconversion of hydrogen and nitrogen intoammonia. This was developed by the Nobelprize laureate Fritz Haber (Figure 1.7), at theKaiser-Wilhelm-Institut in Berlin, and laterapplied to the industrial process by CarlBosch, at BASF (Figure 1.8), who was alsoawarded the Nobel prize. The ammonia cat-alyst consists mainly of iron in combinationwith various adjuvants, and is very difficult toanalyze during its application in the reactor.The structural conditions on the catalyst

surface and in the pores during reaction arenot exactly known. The production of hetero-geneous catalysts is largely the domain of afew manufacturers that have an extensive,mostly empirically acquired, know-how ofcatalyst synthesis. The optimal reaction con-ditions for the ammonia catalyst are quiteharsh (350–520 �C, 300 bar), and it can beeasily deactivated by catalyst �poisons� suchas carbon monoxide or sulfur compounds.Themain advantage of the process, however,is the good separability of the product andcatalyst; the solid catalyst remains in thereactor, while the gaseous ammonia is easilycollected.Homogeneous and heterogeneous catal-

ysis have complementary positions in thechemical industry.Forexample,manymajorindustrial products such as gasoline, sulfu-ric acid and nitric acid are produced viaheterogeneous catalysis, whereas manybasic chemicals and fine chemicals, phar-

Figure 1.6 GeoffreyWilkinson.

Figure 1.7 FritzHaber.

Figure 1.8 Carl Bosch.

1.2 The Different Varieties of Catalysis j7

maceuticals and agrochemicals are pro-duced via homogeneous catalysis. Transi-tion metal catalysts enable reactions that,normally, cannot be carried out in anyother way; examples include hydroformyla-tions (Eq. (1.5)), metathesis (Eq. (1.6)), orC�C-coupling reactions (Eq. (1.7)) (Fig-ure 1.9). Each of these reactions is describedindetail inSection1.3 (seealsoChapters19–31). In these descriptions, the abbreviation[cat] is placed above the reaction�s arrow toindicate that it must be catalyzed; occasion-ally, other abbreviations such as [Pd] or [Rh]are also shown, to indicate palladium- orrhodium-catalyzed reactions.

1.3The Directing Effect of the Catalyst

The catalyst not only has the property topermit a reaction to proceed at all, but inmost cases it also has the ability to direct thereaction towards certain products. A typicalexample of this is the �various reaction pos-sibilities of synthesis gas� (a mixture of carbonmonoxide and hydrogen), as shown inFigure 1.10:. Aqueous iron/chromium or coppercatalysts convert synthesis gas and waterto carbon dioxide and hydrogen.

. Iron- or cobalt-containing �Fischer–Tropsch� catalysts lead to (depending on

reaction conditions) alkanes, alkenes, orlong-chain alcohols.

. Copper/zinc catalysts lead almostexclusively to methanol.

. Ethylene glycol can be produced by usingruthenium catalysts.

. Nickel catalysts afford an entiremethanization to methane.

Hence, the chemical industry is in theposition to prepare a wide product rangefrom the same material basis, simply byselecting the most suitable catalyst.The examples in Figure 1.10 relate almost

exclusively to heterogeneous catalysis(except for the example of glycol synthesis),which frequently employs different metals,or their combination. The homogeneoustransitionmetal catalysis offers still anothervariation possibility, namely the choice ofdifferent complex ligands. This is illustratedin Figure 1.11 by the example of butadienecyclooligomerization (cf. Chapter 22) where-by, using the same catalyst metal (i.e.,nickel) a diversity of butadiene oligomerscan be produced, simply by altering theligand sphere:

. Tricyclohexylphosphine (PCy3) leadspredominantly to4-vinyl-1-cyclohexene(1).

. Triphenylphosphite (P(OPh)3) producesthe eight-membered ring molecule 1,5-cyclooctadiene (2).

+ CO, H2[cat.] H

O

Hydroformylationof alkenes

(1.5)

+[cat.]

+ Alkene metathesis (1.6)

X

+[cat.]

+ HX C-C coupling(Heck)

(1.7)ZZ

Figure 1.9 Reactions, which are only possible with transition metal catalysis.


. With nickel bis(acrylonitrile) andaluminum triethyl AlEt3 the 12-membered ring (3) is formed.

. Nickel allyl complexes form the higherhomologues (4).

. The palladium catalyst Pd(ClO4)2 canyield the four-membered ring (5).

. The five-membered ring (6) is formedwhen using [NiCl(ortho-tolyl)(PEt3)2].

Again, several products can be derivedfrom a single substrate, although the eight-and 12-membered rings are particularlyimportant from an industrial aspect. Thecontrolling possibilities of the ligands arediscussed in detail in Chapters 7 and 9,while themonitoring of reactions is detailedin Chapter 4, which incorporates the �targetsizes� of catalytic reactions.

Water gas shift reaction(+H2O)

Fischer–Tropschreactions

Hydrogen

Alkanes

Alkenes

Methanol synthesis

Glycol synthesisHO–CH2–CH2–OH

Methanization

[Cu/Zn]

[Ru]

[Ni]

[Fe] or [Co]

Alcohols,carboxylic acids

[Fe/Cr] or [Cu], –CO2

CH3OHCO + H2Synthesis gas

CH4

Figure 1.10 Catalytic control of synthesis gas reactions.

n

5

6

1

2

3

4

Figure 1.11 The cyclic oligomers of butadiene.

1.3 The Directing Effect of the Catalyst j9

1.4Catalysis as a Part of �Green Chemistry�

As catalysis provides the ability to produce adesired product without unquestionedbyproducts, it can be seen as a cornerstoneof �green chemistry,� the important princi-ples of which include:. The prevention of waste.. The products shall contain the maximalproportion of reactants; that is, thereaction is to be �atom-economic.�

. The reactions must function withincreased energy efficiencies.

. The usage of renewable feedstocks ispossible.

. Any derivatization reactions, such as theneed for blocking or protecting groups,should be avoided.

. Catalytic agents are superior tostoichiometric agents.

Homogeneous transition metal catalysis,in particular, meets such demands, forexample, it allows the direct C�C-bondingof different building blocks without anyneedless intermediatesteps(seeChapter19).Such catalysis usually functions under mildreaction conditions, such as low tempera-tures (room temperature to 150 �C) and lowpressures. It is also suitable for the conver-sion of renewables (as will be described inChapter 38).An example from the chemical industry

can be used to demonstrate the above-stat-ed principles. After a heavy night�s drink-ing, pills containing ibuprofen can help inthe recovery from a hangover. Ibuprofen isconventionally synthesized from isobutyl-benzene in a six-step synthesis (Fig-ure 1.12, left); three of the six steps involveBrønsted or Lewis acids, while the twoother steps require bases. This leads inev-itably to the production of large quantitiesof salts, the disposal of whichmay create an

unnecessary burden on the environment.In contrast, a novel catalytic pathway ofibuprofen synthesis – as elaborated byHoechst–Celanese (Figure 1.12, right) –

contains only three reaction steps, withoutthe formation of considerable quantitiesof salt:

. The first step – the acylation ofisobutylbenzene in the para position – isstill catalyzed by homogeneous acidcatalysis.

. In the second step, the keto group ishydrogenated to an alcohol byheterogeneous catalysis. The catalystused is recyclable palladium on carbon[Pd/C].

. The third step includes carbonylation ofthe hydroxyl group, leading to thecarboxylic acid by means of carbonmonoxide. The catalyst is a homogeneouspalladium complex.

So, ibuprofen has been synthesized afteronly three steps, and all of the reactantsused – except, of course, the catalysts! –are present in the final product.

1.5Sources of Information about Catalysis

When working through this book, a litera-ture annex will be found at the end of eachchapter, which cites a small selection ofreasonable books, reviews and importantreports. In the appendix of this Chapter, thedetails are provided of several well-knowntextbooks and reference books, that willhelp to deepen the knowledge of homoge-neous transition metal catalysis.In order to be kept up to date, however, it

is essential to monitor relevant �catalysisjournals,� the following of which are recom-mended by the authors.


Homogeneous transition metal catalysis:. Journal of Molecular Catalysis A:Chemical

. Advanced Synthesis andCatalysis

Organometallic chemistry and homoge-neous transition metal catalysis:. Journal of Organometallic Chemistry. Applied Organometallic Chemistry. Organometallics

Ac2O

AlCl3

O

O

COOEt

CHO

NOH

CN

COOH

O

OH

base ClCH2COOEt

H2O / H+

NH2OH

- H2O

Ac2 HFO

H2

[Pd/C]

catalytichydrogenation

CO[Pd2+]

catalyticcarbonylation

Ibuprofen

classic route catalytic route(Hoechst-Celanese)

- 6 Steps- intense salt formation

- 3 steps- 100% atom economically

H2O

H+

isobutylbenzene

Figure 1.12 Comparison of synthesis methods of ibuprofen.

1.5 Sources of Information about Catalysis j11

. Transition Metal Chemistry

. Advances in Organometallic Chemistry

. Topics in Organometallic Chemistry

. Coordination Chemistry Reviews

Catalysis (general, but especiallyheterogeneous):. ACS Catalysis. Catalysis Science & Technolog Today. Advances in Catalysis. Applied Catalysis A: General. Catalysis Letters. Catalysis Reviews: Science andEngineering

. ChemCatChem

. Catalysis Communications

Journals which often also report oncatalysis:. Angewandte Chemie. Chemistry – A European Journal. Journal of the American Chemical Society. Chemical Communications. Green Chemistry. Chemical Reviews. Synthesis. Organic Letters. Tetrahedron. Tetrahedron Letters

. Platinum Metals Reviews (online: www.platinummetalsreview.com)

. Accounts of Chemical Research

. Journal of Organic Chemistry

. Chemie-Ingenieur-Technik

. Science

. ChemSusChem

. Dalton Transactions

. Chimia

Toensurethatnoimportantfindingsarebemissed, it is useful to subscribe to �Catalystsand Catalyzed Reactions,� which is publishedby the Royal Society of Chemistry (see: www.rsc.org/catalysts). This abstract journal ispublished 12 times each year in both printand electronic format, and contains (veryshort!) summaries of recent key publicationson catalysis. A general example is given inFigure 1.13, which contains only the title,authorsandsource,besidesa typical reaction,the catalyst, and important reaction condi-tionsandresults. If anarticle is interesting,ofcourse, the original report must also be con-sidered. The abstracts are indexed by type ofreaction, comparable to Part III of this book.So, if the details of only certain reactions arebeing sought, it is possible to examine therelevant subsections in selective fashion.

OH(i) Au complex

4 examples(13–100% conversion) 94% conversion

11848 Coinage metal complexes with N-heterocyclic carbene ligands asselective cataysts in diboration reaction

R. Corberan; J. Ramirez; M. Poyatos; E. Peris*: E. Fernandez*

Tetrahedron: Asymmetry, 2006, 17(12), 1759-1762

THF, 25 ºC, 60 h O

O

O

OB B

(ii) NaOH, H2O2

OH

Au complexCl

Cl Cl

Cl

Au

n-ButN

n-ButN

NBut-n

NBut-n

Figure 1.13 Constitution of a graphical abstract in �Catalysts and Catalyzed Reactions.�


Today, as catalysis is used and explored sointensively by industry,muchof the recentlyacquired information is not available in�open access literature,� but rather may belocated (at least in part) in patents. None-theless, research details included in patentsmay be obtained from various patent data-bases, that include:. �Espacenet�: This is a European networkof patent databases, which can beaccessed on the internet at www.espacenet.com. It includes more than50 million patents from all around theworld, which are frequently updated.A quick search can include keywords,inventors or companies; in an advancedsearch, the various search terms can belinked together. Forfirst-time visitors �Anintroduction to the database of ideas� isprovided on the portal site.

. �Depatisnet�: This is the database of theGerman Patent and Trade Mark Office(DPMA). It can be found at http://

depatisnet.dpma.de. It is possible tochoose between a �Beginner�s search�and an �Expert search,� or to search forpatent families. When using the�Assisted search,� it is possible to forwardrequests to the German patentinformation system.

. The patent database of the USA isadministered by the �United StatesPatent and Trademark Office,� and islinked under http://patft.uspto.gov.

. Other important web addresses for patentdatabases include:. http://www.wipo.int/pctdb/en/index.jsp. http://pericles.ipaustralia.gov.au/ols/auspat

. http://www.getthepatent.com

. http://www.google.com/patents

. http://www.freepatentsonline.com/search.html

. http://www.ipo.gov.uk/types/patent.htm

. http://www.irossco.com/patentsearching.htm

Take-Home Messages

. Catalysts increase the rate at which achemical system reaches itsequilibrium.. In theory, catalysts are not consumedduring catalytic reactions; in reality, theycan be either destroyed or poisoned.. Catalytic processes are usuallypresented in catalytic cycles.. Catalysts can be divided intohomogeneous and heterogeneouscatalysts. Homogeneous catalysts can bedissolved in the reaction solvent;heterogeneous catalysts form a second,usually solid, phase.. Homogeneous catalysis can befurther subdivided into: acid/base catalysis; enzyme or

biocatalysis; and transition metalcatalysis.. Homogeneous transition metal catalystsare characterized by high activities andhigh selectivities. Transition metalcatalysts can be adapted to the syntheticdemands by changing their ligand field.. Homogeneous transition metalcatalysts have advantages over theheterogeneous catalysts, because oftheir well-known molecularstructure and their reproduciblesynthesis. As homogeneous catalystsare completely soluble, all metalatoms can be catalytically active. Thereare no diffusion problems involved inhomogeneous catalysis.

1.5 Sources of Information about Catalysis j13

Exercise Questions

1.1 Which catalyst did D€obereiner use in his gas lighter?1.2 Draw a general catalyst cycle of the Knallgas reaction!1.3 List five advantages of homogeneous catalysis in comparison to heterogeneous

catalysis.1.4 What is the main problem associated with homogeneous transition metal

catalysis?1.5 How can Wilkinson�s complex be synthesized?1.6 Which products can be obtained catalytically from synthesis gas?1.7 Draw at least three cyclic butadiene oligomers. Note the correct position of the

double bonds. What is their technical importance?1.8 How can a homogeneous transition metal catalyst be varied relatively easily?1.9 Why are there no diffusion problems in homogeneous catalysis?1.10 Which principles of �green chemistry� are met by homogeneous transition

metal catalysis?

Literature

J. F. Hartwig. Organotransition MetalChemistry: From Bonding to Catalysis,University Science Books, 2010.

A. Behr. Catalysis, Homogeneous, Ullmann�sEncyclopedia of Industrial Chemistry,Wiley-VCH, Weinheim, online edition,2010.

R. H. Crabtree (ed.): in: Handbook of GreenCatalysis (ed.: P. T. Anastas), Vol. 1,Homogeneous Catalysis, Wiley-VCH,Weinheim, 2009.

D. Steinborn. Grundlagen der metallorga-nischen Komplexkatalyse [in German]Teubner, Wiesbaden, 1.Edition,2007.

M. Beller, C. Bolm (eds). Transition Metalsfor Organic Synthesis, Wiley-VCH, 2ndedition, 2004. A good reference book fororganic chemists.

P. W. N. M. van Leeuwen. HomogeneousCatalysis – Understanding the Art, KluwerAcademic Publishing, 2004.

T. Horv�ath. Encyclopedia of Catalysis, Wiley-VCH, 6 Volumes, 2003.

B. Cornils, W. A. Herrmann, R. Schl€ogl, C.-H. Wong (eds). Catalysis from A to Z – AConcise Encyclopedia, Wiley-VCH, 2ndedition, 2003.

B. Cornils, W.A. Herrmann (eds). AppliedHomogeneous Catalysis with Organome-tallic Compounds, Wiley-VCH, 2nd edi-tion, 2002. Three volumes; a good

. At first glance, the demandingseparability appears to be adisadvantage of homogeneous catalysis.However, numerous possibleapproaches are available to resolve thisproblem.

. Homogeneous transition metalcatalysis requires only mild conditions,and often allows the selective synthesisof a desired product in a few reaction steps,without creating byproducts. Hence, it is acornerstone of �green chemistry.�


handbook for homogeneous transitionmetal catalysis; a third edition is inpreparation.

J. Tsuji. Transition Metal Reagents andCatalysis – Innovations in Organic Syn-thesis, John Wiley & Sons, 2000.

S. Bhaduri, D. Mukesh. HomogeneousCatalysis – Mechanisms and IndustrialApplications, Wiley-Interscience, NewYork, 2000.

Book series �Topics in OrganometallicChemistry, Springer-Verlag, Berlin, Hei-delberg, 37 volumes, up to 2011. Varioustopics of homogeneous catalysis.

Book series �Catalysis by Metal Complexes,�P. W. N. M. van Leeuwen, B. R. James(eds), Springer-Verlag, Berlin, Heidel-berg, 37 volumes (1976–2011). Books ontheoretical and practical aspects ofhomogeneous catalysis.

Literature j15

part i chemical basics

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